Ferric pyrophosphate hydrate-bf3-mocl5 catalyst and alkylation process



United SW 2,923,750 FERRIC PYnoPHosPHA HYDRATE-BF -M6Cl CATALYST AND ALKYLATION PROCESS I This invention relates to "a catalyst-adapted for coners ion's of Hydrocarbons and processes utilizing the t rs-t. .fl

In U. 2,824,146, there is set out a process foralkylation of hydrocarbons using as the catalyst a system conlisting essentially er ferric pyrephes nate hydrate-3P complex and B Fg. This process requires circulation of BE; in the system and recovery or BF from the product stream. 7 It is obvious that economic advantages exist for Ia" catalyst which does not require the BF circulation.

An object ofithe invention is a analyst or ferric pyrep'n sphete-BF, type, which does no: require addi- 'tibrial BFg. A further object is a solid catalyst containing ferric pyrophosphate hydrate and BF other ohje'ctswill become 'appare'iit in the course of the detailed description of the invention. v i

It has been discovered that an effective catalyst for many hydrocarbon reactions, particularly alky'lation and polymerization, is obtained byfinte'rinirig'lin'g ferric pyrophosphate hydrate-BF, emples, jaslie' matter defined, and molybdenum pentachloride, in a hereinafter defined fatio.

The Catalyst composition consists "essentially of two solid rn'embers. One member is a complex having the empirical formula Fe (P O .aH O.bBF where izf is at leas 3 an b is "from abeu't 0.7a a) Ferric pyrepho'sphate forms hydrates with water, which hydrates iiia y 'Coiltain fr Oi I i 1 to "as many as 18 moles of Water (if hydration per mole of ferric pyrophosphate. It has been fouiid that the catalytically -"e'lfective complex shouldcontai n "at least 3 moles of water of hydration per mole of -ferric pyrophosphate. In general, 'it is preferred that the complex be formed from ferric pyrophosphate hydrate containing from '6 ts armies of "water or hydration per more of ferric pyro hesph'are. Boron triflaaridemust be present in the complex; apparently the BE, eomprexes with the hydrated water to form -a solid material. In I order to attain effective catalytic activity, it is necessary that the, complex contain at least 0;? mole of BF per mole of hydrate water, and preferably the eem rex should contain 1 mole of B1 for each mole of water-ofhydratiq present. To illustrate, when ferric pyrophos'phate .6H 'O is the hydrate, thejcompl'ex containat least 4 moles of B1 and preferably contains 6 molesof BF these two complexes ma' p' written as Fe, P, o ,.6H-,=o:4-BF, and

I v The BF and the hydrate are reacted to form a solid material containing complexed B-F When the salt hydrate and BF are contacted in a closed vessel, the BE, partial pressure drops ver 'rapidlyat first and then gradually approaches a constant value. It appears that "a very rapid reaction between the and some bf the water of hydration takes place. This initially rapid reaction is then followed by a relatively slow reaction between the remaining molecules of hydrate water and additional BF In the case of ferric pyrophosphate containing 11 moles of hydrate water per mole of the salt, it appears that 4 or 5 moles of hydrate water are rapidly reacted.

substituted methylnaphth-a-lenes.

r 2,923,750 Patented Feb. 2,1960

. 2 V However, stirring of finely powdered hydrate salt in the presence of excess BF at about room temperature for a period of about 20 hours, results in the reaction of 1 mole of BF for each mole of hydrate water present in the ferric pyrophosphate hydrate.

. The solid complex of ferric pyrophosphate hydrate and -BF has moderate catalytic activity and may be used for purposes such as polymerizing isobutylene. This complex has no activity for the difficult ethylene-isobutane alkylation reaction. It has been found that a catalyst system of great activity is obtained by intermingling the defined ferric pyrophosphate hydrate-B1 complex with molybdenum pentachloride in a mole ratio of MoClg to ferric pyrophosphate from about 0.5 to about 3 and preferably from about 1.5 to 2. The composition consisting essentially of the defined complex and MoCl in this ratio is very effective for promoting the difiicult ethylene-isobutane alkylation reaction. For less difficult reactions, a compositioncontaining more or less MoCl may be used.

The defined composition of complex and MoCl may be used as such; the composition may be used in'the form of a powder or shaped into pellets. Or, the, catalyst composition may besupported on a carrier such as alumina, pumice, silica, silica alumina and carbon.

The catalyst may be used at any temperature below the temperature at which the salt hydrate decomposes, that is, loss of all its water of hydration. The temperatures of operation may be as low as 25 C. or even lower. Temperatures as high as 150 C. and even higher may be used with some of the hydrates which have relatively high decomposition temperatures. For example,

ferric pyrophosphate .5H O has been heated for 20 hours "keep a substantial portion of the hydrocarbons charged in the liquid state. In general, pressures will be between about 50 and 1000 p.s.i. and preferably between about and 600 p.s.i. for alkylation or polymerization. The reactants in the hydrocarbon charge to the alkylation process are isoparaffin, or an aromatic hydrocarbon and olefin. The olefin contains from 2 to about 12 *carbon atoms. Examples of suitable olefins are ethylene, propylene, butene-Z, hexene and octene; in addition to these, the olefin polymers obtained from propylene and/ or 'butyl'ene are also suitable for use in theprocess, such as codimer, propylene trimer, propylene tetramer and butylene trimer. It is preferred to operate with ethylene or propylene.

The aromatic hydrocarbons must be alkylatable by the particular olefin used. It is self-evident that anaromatic hydrocarbon which contains alkyl substituents positioned so that steric hindrance would prevent or greatly reduce the possibility of alkylation with the particular olefin "should notbesubjected to the process. Examples of particularly suitable aromatic hydrocarbons are benzene, toluene, xylene, trimethylbenzenes, and theother alkyl analogues, such as propyl and butyl,,'the naphthalene aromatic hydrocarbons, such as the mono and di- The isoparaffin reactant is defined as a paraffinic hydrocarbon which has a tertiary hydrogen atom, i.e., paraflins which have a hydrocarbon atom attached to a tertiary carbon atom. Examples of these are isobutane, isopentane (Z-methylbutane), Z-methylpentane, 2-methylhexane, S-methylhexane, 2,3-dimethylbutane (di-isopropyl) and 2,4-dimethylhe xane. Thus the isoparafi'ins usable as i one reactant in the process contain from 4 to 8 carbon atoms.

In the isoparaflin-olefin system, the alkylation reaction is more favored as the mole ratio of isoparaffin to olefin increases. In general, the isoparaffin to olefin mole ratio in the hydrocarbon charge should be at least 1. More than this amount is good audit is desirable to have an isoparaffin to olefin ratio between about 2 and 25 and in some cases more, for example, as much as 50. It is preferred to operate with an isoparafiin to olefin mole ratio of between about 5 and 15.

The presence of non-reactive hydrocarbons in the hydrocarbon charge is not detrimental unless the reactants become excessively diluted. For example, the isoparaflin may also contain isomers of the normal configuration. The olefins may contain paraflins of the same carbon number. Mixtures of 2 or more isoparaffins or 2 or more aromatic hydrocarbons, or 2 or more olefins may be all at one point into the reactor'or it may be introduced at 2 or more points. The alkylation reaction is some what exothermic and temperature control is facilitated by introducing the olefin into the reactor at more than one point.

The contacting of the isoparafiin or aromatic hydrocarbon and the olefin in the presence of the defined catalyst pair is continued until an appreciable amount of alkylate has been formed. In batch reactions, it is possible to virtually extinguish the olefin, i.e., convert substantially 100% of the olefin by a sufficiently long period of contacting. When operating in a continuous flow system, it may be desirable to have a time of contacting such that substantial amounts of olefin are not converted and obtain the complete conversion of the olefin by'a recycle operation. The time of reaction will be determined by the type of hydrocarbons charged, the ratio of isoparaflin or aromatic to olefin, the degree of mixing in the contacting zone and the catalyst usage. A few tests will enable one to determine the optimum time of contacting for the particular system of operating conditions being tried.

The hydrocarbon reaction may be carried out in a reactor which may be a vessel providing for a batch-type reaction, i.e., one wherein the desired amount of isoparafiin or aromatic and olefin are charged to a closed vessel containing the catalyst pair and the vessel then maintained at the desired temperature for the desired time. At the end of this time, the hydrocarbon product mixture and unreacted materials are withdrawn from the vessel and processed to separate the alkylate product from the unreacted materials and lower and higher molecular weight materials. The reaction may be carried out in a fixed bed operation wherein the reactants are flowed through a bed of catalyst, the space velocity being controlled so that the desired amount of reaction is obtained during the passage of the reactants through the bed. Under some conditions, a moving bed of catalyst may be utilized. In still another set of circumstances, a fluidized bed may be utilized with the incoming stream of reactants providing the energy for the fluidization of 2,923,750 A r ,7 a

. 4 the catalyst. Other methods of operation common in the catalytic refining aspects of the petroleum industry utilizing solid catalyst may be readily devised.

Tests For purposes of illustration, the results of comparable tests using a catalyst composition of the invention and the complex alone are set out below.

The tests were made as follows: g. of

and 200 ml. of isobutane were charged to a dry 4-1iter carbon steel bomb. The bomb was then placed in an ice bath and cooled. BF was slowly added with care to avoid overheating of the salt as a result of the exothermic reaction. The bomb was gradually pressured to 250-300 p.s.i.g. with BE, and allowed to stand at least 12 hours, after which the bomb was repressured and evacuated.

The M0Cl was added, when used, andthen 1000 g. of

a blend of isobutane and ethylene were charged (3/1 molar U0). The bomb was rocked 20 hours at 20l-30 C. and then sampled for Podbielniak distillation analysis.

Test 1: Only 18 weight percent of alkylate were obtained when only ferric pyrophosphate hydrate-BF; complex was present as catalyst in the reactor.

Test 2: In this test where the catalyst composition consisted of ferric pyrophosphate .9H O.9BF and molybdenum pentachloride in a mole ratio of 0.6 mole of MoCl per 'mole of ferric pyrophosphate, the alkylate yield of material boiling above pentane was 113 weight percent based'on ethylene charged.

Test 3: This test was carried out as in Test 2, except that the mole ratio of M001 to pyrophosphate was 1.7. In this test, the C yield was 167 weight percent based on ethylene charged.

Thus having described the invention, what is claimed is:

1. A composition consisting essentially of (1) a complex having the empirical formula Fe (P O .aH O.bBF, where a is at least 3 and b is from about 0.7a to a" and (2) molybdenum pentachloride, where the molar ratio of said chloride to said pyrophosphate is from about 0.5 to about 3.

2. A composition consisting essentially of (1) the complex Fe (P O .9H O.9BF and (2) MoCl where the mole ratio of said chloride to said pyrophosphate is from about 1.5 to 2.

3. An alkylation process comprising contacting an alkylatable hydrocarbon with an olefin, at a temperature below the temperature of decomposition of ferric pyrophosphate hydrate and at a pressure sufiicient to maintain a substantial portion of said reactants in the liquid state,

where a is at least 3 and b is from about 0.7a to a References Cited in the file of this patent UNITED STATES PATENTS Upham Sept. 3, 1946 Kelly a a1. Feb. 18, 1958 

1. A COMPOSITION CONSISTING ESSENTIALLY OF (1) A COMPLES HAVING THE EMPIRICAL FORMULA FE4(P207)3.AH2O.BBF3 WHERE "A" IS AT LEAST 3 AND "B" IS FROM ABOUT 0.7A TO "A" AND (2) MOLYBDENUM PENTACHLORIDE, WHERE THE MOLAR RATIO OF SAID CHLORIDE TO SAID PYROPHOSPHATE IS FROM ABOUT 0.5 TO ABOUT
 3. 3. AN ALKYLATION PROCESS COMPRISING CONTACTING AN ALKYLATABLE HYDROCARBON WITH AN OLEFIN, AT A TEMPERATURE BELOW THE TEMPERATURE OF DECOMPOSITION OF FERRIC PYROPHOSPHATE HYDRATE AND AT A PRESSURE SUFFICIENT TO MAINTAIN A SUBSTANTIAL PORTION OF SAID REACTANTS IN THE LIQUID STATE, IN THE PRESENCE OF A CATALYST CONSISTING ESSENTIALLY OF (1) A COMPLEX HAVING THE EMPIRICAL FORMULA 